Vinyl resin compositions



Patented Dec. '2, 1941 2,264,625 RESIN 'GIOMPO'SITIONS Arthur 1;. Doolittle, South Charleston, w. Va., assignor to Carbide and-Carbon Chemicals Corporation, a 'corporation of- New York N0 Drawing. ApplicationxMay 31,1939,

. Serial'No. 276,584

(Cl. zoo- 32) Claims.

The invention relates to vinyl resin *compositions of particular usefulness in'the preparation of lacquers, varnishes, dopesandother-coating and finishing materials.

in compounding vinyl resin compositions.

It isv especially concerned with new and improved solvents :for'use While vinyl resins of variouskinds have'been proposed for and used in surface coating 'compositions, the inherent physical and chemical characteristics of these resins have presented;

many problems in the formulating of satisfactory lacquers and the like. An :important 'one of these problems has arisen through the difilculty of obtaining suitable and proper solvents for these resins. Many compounds knowntohave a solvent action on other kinds of lacquergums and resins will not dissolve the'vinyl resins, or if'they do exhibit solvent power for the latter'resins, they are often deficientin-other characteristics. A

high boiling solvent suitable for use in vinyl resin lacquers should dissolve a highcontent'of resin hydrocarbonderivatives suitable for thinning in a slowlyevaporating mixture.

A very valuable and important characteristic of these'new solvents resides in their ability to -form solutions of certain vinyl resins high in solids concentration without encountering a 'thixotrop'ic effect or gellation. Solutions of resin of the type formed by conjoint polymerization of without exhibiting troublesome gellation. It.

should permit dilution with substantial quantities of cheaper hydrocarbon diluents, and should not deteriorate on storage. Waterinsolubility'is.

a further desirable property.

It is an object of this invention to provide solvent materials for vinyl resins having all of the above-mentioned desirable properties, and to produce thereby improved vinyl resin lacquers, varnishes, and other coating compositions.

I have found that certain cyclic ketones, in particular isophorone and di-hydroisophorone, have a marked solvent-power for'vinyl resins, and in addition exhibit the other properties requiredifor their satisfactory use vin lacquer thinner "formulae. Isophorone, which may :also be termed 3,5,5-trimethyl n -cycl'ohexenone, can be -forme'd from the condensation of acetone in thepresence of suitable catalysts, such-as lime or sodium ethylate, and by hydrogenation of this compound the saturated product, di-hydroisophorone, .is formed. Both of the compounds'are liquids of substantially water-white'or faintly yellow -color.'

They are water insoluble and 'have=a.very'high boiling point. .lsophorone' boils at about 205 C. to 217 C., and the saturated derivative at a slightly lower temperature. The compounds have a very slow evaporation rate which is effective in improving the flowing and leveling properties of a vinyl resin lacquer by maintaining a maximum fluidity in an applied 'surface' fllmx-as the thinner components evaporate-on drying. In formulating thinner compositions these solvents will permit of substantial dilution with inexpena=vinyl halide *with a vinyl ester normally show the'viscosityefiect of thixotropism to a considerable degree, which has necessitated heretofore a limitation in the solids to solvent ratio well below the actual point of gellation to insure a sat- I isf-acto'ryfluid condition. With isophorone or dihydroisophorone as the solvent these resins may be dissolved in concentrations considerably higher,-and very close to the gel point, without exhibitingianyappreciable tendency toward thixotropism. For example, 25% solutions of a conjointly polymerizedproduct of vinyl chloride and vinyl acetate in a mixture of isophorone, and

'45%"xylene are still in a satisfactory fluid state,

whereas with a solvent of an acetone-toluene mixture in corresponding proportions, not more than 20% :of the same resin may be introduced without causing abnormal viscosity effects. The new solvents will thus permit a wider and greater formulating range of solid to solvent ratios than has heretofore been possible with prior vinyl resin solvents.

A further. phenomenon is shown by both solvent materials, which is quite unusual, and consists in the:fact that at a constant vinyl resin concentration in the solvent a decreased solution viscosity is shown as diluent is added up to a certain point, and the'solution viscosity then increases as more diluent is added. This provides ameans whereby a solution of the resin in a mixture of either of these solvents and a suitable diluent, such as xylene, can be made up with a lower viscosity than a solution of the same solids content in the solvent alone, and presents distinct advantage in formulating lacquers for rollercoating application, through the ability to achieve improved flow-out with a minimum viscosity.

The :vinyl "resins'with which the invention is directlyconcerned include those which may be formed bypolymerization of a vinyl halide, a vinyl ester, suchasvinyl acetate, or by the conjoint polymerization of a vinyl halide with a vinyl Polymerized vinyl chloride, and the product resulting f-rom conjointly'polymerizing vinyl chlo- "rideand'vinyl acetate, in proportions of about sive non-solvent diluents, such as :xylene, or other to parts by weight of vinyl chloride to from 40 about 80% to 90% by weightofvinyl chloride,

and having an average molecular weight f ffrom about 8,000 to 12,000, as estimated from the specific viscosity of dilute solutions according to a. Staudingers method. The method of forming the vinyl resins forms no part ofthepr'e'sent invention, and they may be prepared in any mann er knownto the art. .HV; ft} In a complete thinner formula the actualp portions of both the isophorone and di-hydro isophorone may be varied ov'era. wide range, an

a number of factors. The particularvinylresin employed, the nature of the other solid ingredients in the lacquer, the methodof application suitable solvent requirements, which in addition are usually maintained within the most economieal limits. Because of their high boiling point, I

thesolvents are of preferred' use injthfe'formulating of'lacquers for application while hot or by means of roller-coating, or for the'prep'ara tion of graining inks,'st enci1 pas'te'sja'nd likefcompositions.

group consisting of isophorone and di-hydroisophorone.

2. A composition of matter essentially comprising a. polymerized vinyl ester resin dissolved in a solvent containing a member of the group consisting of isophorone and di-hydroisophorone as an essential solvent material.

: 3. composition ,of matter essentially com- .fprisin gaviriyl ester resincontaining a polymerized vinyl halide dissolved in a solvent containing a member of the group consisting of isophorone .and di-rhydroisophorone as an essential solvent material;

4. A-.'vinyl;resin composition essentially compr-isingxpolymerized vinyl chloride dissolved in a solvent containing a member of the group consisting of isophorone and di-hydroisophorone as anessentiah solvent material.

the most desirable concentrations will depend on 5. A vinyl resin composition essentially comprising polymerized vinyl acetate dissolved in a .solventpontaining. a member of the group con- Representativej lacquer, compositions 1:

within the scope of the invention are shown by i f the following two formulae, in' 'whichfthe vinyl resin base is thefconjointly polymerized. product about 80% to 90%. of vinyl chloride,

of vinyl chloride and vinyl acetate co'ntaining Pigmented xclear l u r, a q e Percen't by Perccnt by 'weight weight Vinyl resin.. -..14.5

'Iricresyl phosphate. 6. 4 Isonhoronc. 11.2 Xylene 22.4 White lead 7.'4 j Antimony oxidel 1.6 Titanium dioxide...... 14.1

Methyl amylketnne. 5.6 Tetrahydronephthalene. 16.8

As shown bythe above examples, otherm'ate rials of a solvent action onthe resin may be used fa ting of isophorone and di-hydroisophorone as and the required use of the coating composition, must all be considered in determiningthe most 2.1.

aihlessehtial, solvent. material.

1 6,.; 1. resin composition essentially comprising .aQresin substantially identical with that resulting from theponjoint polymerization of a vinyl -halide ;with- .a vinyl ester'of an aliphatic aci'd dissolved-inasolvent containing a member of thegroup consisting of isophorone and di- 0...

7-. A vinyl resin coating composition essentially hydroisophoroneas an essential solvent material.

comprisinga resin substantially identical with that resulting from. the conjoint polymerization I of vinyl chloride and vinyl acetate and containing from 80% to.90% by weight of vinyl chloride, =.dissolyed-in a solvent containing a member of the groupconsisting of isophorone and di-hydroisophorone as an essential solvent material.

in conjunction with those here disclosed without departing from the spirit of this invention, and

the usual lacquer modifying ag'ents,"such 'asjstabilizers, plasticizers, dyes, pigments, andtlie like,

can be included Without effect upon the essential 1 ti'ally" comprising a resin substantially identical with that'resultingfrom'the conjoint polymeradvantages afiorded by these new solventcompounds. Numerous mo'difications in a'c'o'rnplete :8. -A yinyl-resin coating composition essentially comprising:a resinasubstantially identical with that resulting 'fromiheconjoint polymerization of' vinyl chloride'and vinyl acetate and containring from. %..to 19.0% by. weight of vinyl chloride, dissolvedin.a-'thinnereontaining as an essential ,solvent-material'a member of the group consisting of isophorone and di-hydroisophorone, and

s .a wolatile hydrocarbon diluent.

9. A vinyl resin coating composition essentially comprising a resin substantially identical with thatresulting from the conjoint polymerization of vinyl chloride 'andvinyl acetate and containingfrom'80 to by weight of vinyl chloride, 'dis'solvedin-fa thinner containing isophorone as jan=essentialfjsolvent material and a volatile non- 'solvent 'hydrocarbon diluent.

101A vinyl 'resin coating composition essenization1 ofjvinyljehloride'and vinyl acetate and 'contai'ningfrom 80%" to 90% "by weight of vinyl fnn onqe; dissolved in a thinner containing di- 1 hydroisophorone'asan essential solvent material and 'a volatilef non' solvent hydrocarbon diluent.

' K. DOOLITTLE. 

